Claims:CLAIMS
1. An emulsion comprising:
a functional additive present within a polymeric shell, wherein the functional additive comprises compounds having at least one functional group selected from aldehyde, amine, diazonium and isocyanate and wherein the polymeric shell comprises repeat units of ethylenically unsaturated monomer and at least one ethylenically unsaturated monomer having an acetoacetate functionality.

2. The emulsion of claim 1, wherein the ethylenically unsaturated monomer having the acetoacetate functionality is 2-acetoacetoxyethyl methacrylate monomer (AAEM).
3. The emulsion of claim 1, wherein the ethylenically unsaturated monomer comprises acrylic acids, methacrylic acids, their monoesters, or diesters.
4. The emulsion of claim 3, wherein the monoesters comprise methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, glycidyl methacrylate, methyoxybutenyl methacrylate, isobornyl methacrylate, hydroxybutenyl methacrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, or hydroxyethyl(meth)acrylate.
5. The emulsion of claim 3, wherein the diesters comprise ethylene glycol di(meth)acrylate, allyl(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4 butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol dimethacrylate, or trimethylolpropane tri(meth)acrylate.
6. The emulsion of claim 1, wherein the functional additive comprises at least one of methyl anthranilate, cinnamaldehyde, diaminobutane, cadaverine, indole, 2-(5-(5-[Cyano-(9,9-dimethyl-1,4-dioxa-7-aza-spiro[4.4]non-7-en-8-yl)-methylene]-3,3-dimethylpyrrolidin-2-ylidene methyl)-3,3-dimethyl-ë1-pyrrolin-5-ylidenemethyl-4,4,5-trimethyl-ë1-pyrroline-5-carbonitrile, 3,4-dimethyl-3-cyclohexene-1-carbaldehyde’ 3-methyl-2-cyclohexen-1-yl)acetaldehyde, 3,7-dimethyl-2,6-octadienal, 7-hydroxy-3,7-dimethyl- octanal, isomethyl ionone, a-methyl-a-(p-tert.-butylphenyl)- propanal, 9-octadecenal, 1-(2,3,4,7,8,8a-hexahydro-3,6,8,8-tetram ethyl-1H-3a,7-methanoazulen-5-yl)- ethanone, 2-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)butanal, 4-(benzyloxy)-3-hydroxybenzaldehyde, benzhydrazide, benzyl hydrazine, methyl anthranilate, methyl N-formylanthranilate, 2-[(1,1-di(trifluoromethyl)propylamino] (hydroxy)methylenamino-, methyl ester, and 1-(1-naphthyl)hydrazine.
7. The emulsion of claim 1, wherein the functional additive provides a fragrance and a reaction product of the functional additive and at least one ethylenically unsaturated monomer having an acetoacetate functionality provides formaldehyde abating capability when used in formaldehyde abating indoor paints.
8. The emulsion of claim 7, wherein the formaldehyde abating capability is in a range of about 50 % to about 90%. .
9. The emulsion of claim 7, wherein the fragrance is released slowly over a period of time.
10. The emulsion of claim 1, wherein the functional additive present within the polymeric shell is covalently bonded with ethylenically unsaturated monomers having an acetoacetate functionality present in the polymeric shell.
11. The emulsion of claim 1, wherein the functional additive present within the polymeric shell further comprises at least one of hydroxyl, ester, ketone, allyl, and vinyl functional groups.
12. The emulsion of claim 11, wherein hydroxyl, ester, and ketone functional groups are unreactive with the acetoacetate functionality of the polymeric shell.
13. The emulsion of claim 11, wherein the functional additive provides a pleasant smell, antifungal, anti-algal and anti-bacterial properties.
14. The emulsion of claim 1, wherein the emulsion comprises solids in a range of about 20 to about 70 weight%.
15. The emulsion of claim 14, wherein the emulsion comprises about 50 weight% of solids.
16. The emulsion of claim 1, wherein the emulsion comprises particles of a size in a range of about 30 nm to about 1000 nm.
17. The emulsion of claim 16, wherein the emulsion comprises particles of a size in a range of about 150 nm to about 300 nm.
18. The emulsion of claim 1, wherein the emulsion has a pH in a range of about 4 to about 10.
19. The emulsion of claim 1, wherein the functional additive is encapsulated within the polymeric shell, mixed through and through the polymeric shell, or is impregnated with the polymeric shell.
20. A method of preparing an emulsion, the method comprising:
charging a reaction vessel with monomers and a functional additive, wherein the monomers comprise repeat units of ethylenically unsaturated monomers, and wherein the functional additive comprises compounds having at least one functional group selected from aldehyde, amine, diazonium and isocyanate functional groups;
emulsifying the monomers and the functional additives with demineralized water and surfactants to form a pre-emulsion;
heating a first portion of the pre-emulsion and an initiator solution to form latex seed particles;
adding a second portion of the pre-emulsion and the latex seed particles to form a mixture;
adding the mixture with at least one ethylenically unsaturated monomer having an acetoacetate functionality; and
cooling to ambient temperature.
21. The method of claim 20, wherein the ethylenically unsaturated monomer having the acetoacetate functionality is 2-acetoacetoxyethyl methacrylate monomer (AAEM).
22. The method of claim 20, wherein the ethylenically unsaturated monomer comprises methacrylic acid, methyl methacrylate (MMA), butyl methacrylate (BMA), and 1,4-butanediol dimethacrylate (BDDMA).
23. The method of claim 22, wherein the BDDMA is present in a range of 0.05-1 wt% of the emulsion.

, Description:FORM 2

THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003

COMPLETE SPECIFICATION
(Section 10, rule 13)

“FORMALDEHYDE ABATING FRAGRANT EMULSION”

Asian Paints Limited
Asian Paint Research and Technology Centre, Plot No. C -3B/1. TTC Industrial Area, MIDC Pawane, Thane Belapur Road, Navi Mumbai – 400703

The following specification particularly describes the invention and the manner in which it is to be performed

FORMALDEHYDE ABATING FRAGRANT EMULSION

FIELD

[001] The invention is generally directed to a fragrant emulsion. In particular, embodiments of the present technique are directed to a fragrant emulsion that retains formaldehyde abating capability of an indoor air purifying paint.

BACKGROUND
[002] Exposure to formaldehyde may cause health effects in some individuals. The severity of symptoms may depend upon the concentration and duration of formaldehyde exposure. Formaldehyde abating indoor paints have low volatile organic compounds (VOC), green labelled, and act as formaldehyde scavengers. However, when fragrant materials are added to the formaldehyde abating paints, they lose their formaldehyde absorbing ability by about 20%. Therefore, there is a need to formulate an emulsion that can impart fragrance to the formaldehyde abating paints without compromising on the formaldehyde absorbing ability.
SUMMARY
[003] The following summary is illustrative only and is not intended to be in any way limiting. In addition to the illustrative aspects, example embodiments, and features described, further aspects, example embodiments, and features will become apparent by reference to the drawings and the following detailed description.
[004] Briefly, according to an example embodiment, an emulsion is provided. The emulsion comprises a functional additive present within a polymeric shell, wherein the functional additive comprises compounds having at least one functional group selected from aldehyde, amine, diazonium and isocyanate and wherein the polymeric shell comprises repeat units of ethylenically unsaturated monomer and at least one ethylenically unsaturated monomer having an acetoacetate functionality.
[005] According to another example embodiment, a method of preparing an emulsion is provided. The method comprises charging a reaction vessel with monomers and functional additives, emulsifying the monomers and the functional additives with demineralized water and surfactants to form a pre-emulsion, heating a first portion of the pre-emulsion and an initiator solution to form latex seed particles, adding a second portion of the pre-emulsion and the latex seed particles to form a mixture, adding the mixture with 2-acetoacetoxyethyl methacrylate monomer (AAEM); and cooling to ambient temperature. The monomers comprise methyl methacrylate (MMA), butyl methacrylate (BMA), methacrylic acid (MAA) and 1,4-butanediol dimethacrylate (BDDMA). The functional additive comprises compounds having at least one functional group selected from aldehyde, amine, diazonium and isocyanate.
DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS
[006] This disclosure is not limited to the particular systems, devices and methods described, as these may vary. The terminology used in the description is for the purpose of describing the particular versions or embodiments only and is not intended to limit the scope.
[007] Embodiments of the present invention relate to a fragrant emulsion and a method of preparing the fragrant emulsion. It should be noted that the fragrant emulsion, unlike other existing fragrant emulsions, retains the formaldehyde abatement capacity of indoor air purifying paints.
[008] The fragrant emulsion includes a functional additive present within a polymeric shell. In some examples, the functional additive includes compounds having at least one functional group selected from aldehyde, amine, diazonium and isocyanate. Further the polymeric shell includes repeat units of ethylenically unsaturated monomer and at least one ethylenically unsaturated monomer having an acetoacetate functionality. Each of these will be described in greater detail below.
[009] In this embodiment, the fragrant emulsion includes a fragrance core surrounded by a polymeric shell. Further, the fragrant emulsion may include a functional additive present within the polymeric shell. It should be noted that the functional additive may be within the polymeric shell, may be encapsulated, may be mixed through and through, may be impregnated or may be bonded. In some examples, the fragrance is made up of natural or synthetically derived organic compounds including aldehyde, amide, amine, carboxyl, hydroxyl, ketone or ester functional groups. Moreover, fragrances may have any desired odor such as woody/earthy, sandalwood, civet, patchouli oil, floral fragrance, desirable fruity odors, or the like.
[0010] The functional additives such as described above, especially aldehyde, amine, diazonium and isocyanate functional group containing organic compound, besides providing fragrance when added to paints, are prone to react with active methylene hydrogen groups generally present in the indoor paints. These methylene hydrogen groups are predominantly the formaldehyde absorbing sources in the paints. This may result in an internal scavenging of the formaldehyde absorbing source. As a result, formaldehyde abating capacity of the formaldehyde abating paint from indoor air may be reduced. In an embodiment, a specialty monomer is added in the polymeric shell to consume fragrant functional groups, particularly aldehyde, amine, diazonium and isocyanate functional groups. This addition of the specialty monomer enhances the formaldehyde abatement properties of fragrant emulsion. One example of the specialty monomer is 2-acetoacetoxyethyl methacrylate (AAEM). However, other specialty monomers having similar properties may be envisaged.
[0011] Further, the proposed fragrant emulsion may provide a higher encapsulation efficiency, slow release of the fragrance and cost advantage in emulsion formulations besides improving the formaldehyde abating capacity of the indoor air purifying paints.
[0012] The process of making the fragrant emulsion, specific ingredients and their concentration and covalent bonding of the fragrant functional additives with the specialty monomer (e.g., AAEM) are key parameters to achieve the targeted properties of the emulsion.
[0013] In one embodiment, ethylenically unsaturated monomer having acetoacetate functionality is 2-acetoacetoxyethyl methacrylate monomer (AAEM). The emulsion further includes esters of acrylic or methacrylic acid. The esters may include methyl methacrylate (MMA), butyl methacrylate (BMA), and 1,4-butanediol dimethacrylate (BDDMA). Methacrylic acid is a functionalized ethylenically unsaturated monomer. Methyl methacrylate (MMA) and butyl methacrylate (BMA) are ethylenically unsatured monomer. 1,4-butanediol dimethacrylate (BDDMA) is a polyethylenically unsaturated monomer.
[0014] The ethylenically unsaturated monomer comprises acrylic acids, methacrylic acids, their monoesters, or diesters. The monoesters comprise methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, isoprene, octyl acrylate, octyl methacrylate, iso-octyl acrylate, iso-octyl methacrylate, glycidyl methacrylate, methyoxybutenyl methacrylate, isobornyl methacrylate, hydroxybutenyl methacrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, or hydroxyethyl(meth)acrylate. The diesters comprise ethylene glycol di(meth)acrylate, allyl(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4 butanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, glycerol dimethacrylate, or trimethylolpropane tri(meth)acrylate.
[0015] The functional additive may include at least one of methyl anthranilate, cinnamaldehyde, diaminobutane, cadaverine, indole, 2-(5-(5-[Cyano-(9,9-dimethyl-1,4-dioxa-7-aza-spiro[4.4]non-7-en-8-yl)-methylene]-3,3-dimethylpyrrolidin-2-ylidenemethyl)-3,3-dimethyl-ë1-pyrrolin-5-ylidenemethyl-4,4,5-trimethyl-ë1-pyrroline-5-carbonitrile,3,4-dimethyl-3-cyclohexene-1-carbaldehyde’ 3-methyl-2-cyclohexen-1-yl)acetaldehyde, 3,7-dimethyl-2,6-octadienal, 7-hydroxy-3,7-dimethyl- octanal, isomethyl ionone, a-methyl-a-(p-tert.-butylphenyl)- propanal, 9-octadecenal, 1-(2,3,4,7,8,8a-hexahydro-3,6,8,8-tetram ethyl-1H-3a,7-methanoazulen-5-yl)-ethanone,2-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)butanal,4-(benzyloxy)-3-hydroxybenzaldehyde, benzhydrazide, benzyl hydrazine, methyl anthranilate, methyl N-formylanthranilate, 2-[(1,1-di(trifluoromethyl)propylamino] (hydroxy)methylenamino-, methyl ester, and 1-(1-naphthyl)hydrazine.
[0016] The functional additive may include at least one of methyl pentanoate, 2-ethyl-2,3,3-trimethyl- Butanoic acid, a & ß-Pinene, a & ß-Phellandrene’ a & ß –Myrcene, 1-methoxy-2-methyl- Benzene, a & ß Limonene, Eucalyptol, a & ß-terpineol, 2,6-dimethyloct-7-en-2-ol, Allyl 2-ethyl butyrate, methyl ester Benzoic acid, Linalool, Phenylethyl Alcohol, Isopulegol acetate, phenylmethyl ester Acetic acid, Geraniol, 4-tert-Butylcyclohexyl acetate, Eugenol, Longifolene, verdyl acetate, 2-methoxy Naphthalene, a & ß-Bisabolene, Humulene, Bulnesene, Lilial, 2-Methylbutyl salicylate, Citronellol, isocitronellol, methyl 3-oxo-2-pentylcyclopentaneacetate, Patchouli alcohol, Globulol, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, Galaxolide, Versalide, Tonalid, Musk ketone, 3-Hexen-1-ol acetate, Camphene, and Cymene.
[0017] In this embodiment, the emulsion has a formaldehyde abating capability in a range of about 50 % to about 90%. As described above, the fragrance from the emulsion releases slowly over a period of time. Here, the functional additive is covalently bonded with ethylenically unsaturated monomers having an acetoacetate functionality. Moreover, the emulsion comprises solids in a range of about 20 weight % to about 70 weight%. In this embodiment, the emulsion includes about 50 weight% of solids and has particles of a size in a range of about 30 nm to about 1000 nm. In some examples, the emulsion preferably includes particles of a size in a range of about 150 nm to about 300 nm. Moreover, the emulsion has a pH in a range of about 4 to about 10.
[0018] The functional additives aldehyde, amine, diazonium and isocyanate functional groups containing organic compound present within the polymeric shell covalently bond with AAEM present in the shell. This ensures providing fragrance encapsulated latex without compromising the formaldehyde abating capability of the paints. This also ensures slow release of fragrance over a period of time, which could be days, months or years.
[0019] The functional additive present within the polymeric shell further comprises at least one of hydroxyl, ester, ketone, allyl, and vinyl functional groups. The hydroxyl, ester, ketone, allyl, vinyl functional groups are essential compounds for providing fragrance to a paint. The hydroxyl, ester, ketone functional groups are unreactive with the acetoacetate functionality of the polymeric shell and remain within the polymeric shell. These functional additive provides a pleasant smell, antifungal, anti-algal and anti-bacterial properties when used in an indoor paint.
[0020] FIG. 1 illustrates an example process 100 of forming the emulsion. At block 102, a reaction vessel is charged with monomers and functional additives. In this example, the monomers include methyl methacrylate (MMA), butyl methacrylate (BMA), methacrylic acid (MAA) and 1,4-butanediol dimethacrylate (BDDMA). Moreover, the functional additive includes compounds having aldehyde, amine, diazonium and isocyanate functional groups. At block 104, the monomers and the functional additives are emulsified with demineralized water and surfactants to form a pre-emulsion. At block 106, a first portion of the pre-emulsion and an initiator solution is heated to form latex seed particles and a second portion of the pre-emulsion and the latex seed particles are added to form a mixture (block 108). At block 110, the mixture is added with 2-acetoacetoxyethyl methacrylate monomer (AAEM) and cooled to ambient temperature (block 112). In this example, a micro biocide is added for in-can preservation of the emulsion after cooling the mixture. In this example, forming the pre-emulsion comprises charging the monomers and the functional additives into a first reaction flask and adding contents of the first reaction flask to a second reaction flask comprising the surfactants, and a 0.1 weight% of sodium bicarbonate solution, wherein adding is carried out at ambient temperature under stirring for about 30 minutes.
EXAMPLES
[0021] The present invention will be described below in further detail with examples and comparative examples thereof, but it is noted that the present invention is by no means intended to be limited to these examples.
[0022] The Bali blue fragrance, (from Givaudan company) comprising more than fifty volatile organic compounds with different polarities, was embedded in nanoparticles by using emulsion polymerization process starting with a homogeneous mixture having monomers and fragrant functional additives. This mixture was subsequently emulsified in water using surfactants. The polymerization was proceeded by a seeded semi batch emulsion polymerization process. After polymerization, stable latexes were obtained. The processes of making fragrant emulsion, specific ingredients concentrations and covalent bonding of the fragrance particle with 2-acetoacetoxyethyl methacrylate (AAEM) monomer / acetoacetamide (AAM) additive in the polymer shell are key parameters to achieve the formaldehyde abatement properties of fragrance encapsulated emulsion. In some examples, AAEM reacts with aldehyde, amine, diazonium and isocyanate functionality of fragrance composition making them unavailable for further reactions. Thereby it improves formaldehyde abatement of the paint even if encapsulation fragrance is used.
[0023] A one liter glass kettle equipped with a mechanical stirrer, reflux condenser, thermometer and inlet tube for pre emulsion feeding was placed in a water bath. The demineralized water, Rhodafac 610/A25, and Atpol 5731/70N were added to the glass kettle. The mixture was then gradually heated to a temperature of about 80° C while stirring at a speed of about 200 revolutions per minute (rpm). Two solutions were separately prepared in two flasks. A first solution was prepared by adding an initiator, potassium persulfate (PPS), and water, and a second solution was prepared by adding monomers, functional additives, a surfactant, a buffer and water to form a pre emulsion. Pre emulsion was actually prepared in two steps. The monomers and fragrant functional additives were taken in a flask and then this mixture was slowly added to another flask containing a surfactant, a buffer and water. The addition was done under stirring and stirring was continued for about 30 minutes at room temperature.
[0024] Further, about 5% of the pre-emulsion prepared as above was added to the kettle at a temperature of about 80?C, followed by addition of the initiator solution. The mixture was allowed for about 15 minutes to produce latex seed particles. After 15 minutes, remaining pre-emulsion was fed into the reaction kettle over a period of 240 minutes. After 120 minutes of pre emulsion feeding, AAEM monomer was added to the kettle. Subsequently, once the feeding was complete, a chaser solution of tert-butyl hydroperoxide (TBHP) and sodium formaldehyde sulfoxylate (SFS) were added separately into the kettle. The reaction was held for about 45 minutes and subsequently terminated by lowering the temperature to room temperature. After cooling the reaction mixture, Amp-95 neutralizer was added to the reaction kettle. The resulting emulsion was then filtered through 80 nylon-mesh.
[0025] Tab1e 1 summarizes the ingredients used for preparing the emulsion of three different sets of experiments. Experiment 1 did not use any AAEM whereas Experiment 2 and Experiment 3 used about 2% and about 3% of AAEM respectively.
TABLE 1
Material Exp 1
(%) Exp 2
(%) Exp3
(%)
DMW 44.6 44.6 44.6
Rhodafac RS 610 A25 2.8 2.8 2.8
Atpol 5731/70N 1.5 1.5 1.5
PPS 0.3 0.3 0.3
SBC 0.1 0.1 0.1
MMA 37 36 35
BMA 1 1 1
MAA 1 0.75 0.75
BDDMA 0.5 0.25 0.25
Methacrylamide 0.5 0 0
AAEM 0 2 3
BDDMA 0.5 0.25 0.25
Bali Blue 10 10 10
TBHP 0.1 0.1 0.1
SFS 0.1 0.1 0.1
AMP-95 0.5 0.5 0.5

Methyl methacrylate (MMA)
Butyl methacrylate (BMA),
Methacrylic acid (MAA),
2-acetoacetoxyethyl methacrylate (AAEM),
1,4-butanediol dimethacrylate (BDDMA),
Bali Blue fragrance,
Sodium bicarbonate (SBC),
Potassium persulfate (PPS),
Demineralized water (DMW).
[0026] Tab1e 2 summarizes the formaldehyde abatement capability of the emulsion of three different sets of experiments. As can be seen, the results indicate that Experiment 3 having about 3% AAEM has about 82% of formaldehyde abating capability.
TABLE 2
Properties Exp 1
Exp 2
Exp3
Solid (%) 49 49 49
Particle size (nm) 220 195 185
pH 8.5 8.5 8.5
%HCHO abatement (lab test) 64 72 82

[0027] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
[0028] While various compositions, methods, and devices are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions, methods, and devices can also “consist essentially of” or “consist of” the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.
[0029] With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.
[0030] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases at least one and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases one or more or at least one and indefinite articles such as “a” or an (e.g., “a” and/or “an” should be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase “A or B” will be understood to include the possibilities of “A” or “B” or “A and B.”
[0031] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.
[0032] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as “up to,” “at least,” and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 cells refers to groups having 1, 2, or 3 cells. Similarly, a group having 1-5 cells refers to groups having 1, 2, 3, 4, or 5 cells, and so forth.
[0033] Various of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations or improvements therein may be subsequently made by those skilled in the art, each of which is also intended to be encompassed by the disclosed embodiments.
[0034] While only certain features of several embodiments have been illustrated, and described herein, many modifications and changes will occur to those skilled in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of inventive concepts.
[0035] The afore mentioned description is merely illustrative in nature and is in no way intended to limit the disclosure, its application, or uses. The broad teachings of the disclosure may be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent upon a study of the drawings, the specification, and the following claims. It should be understood that one or more steps within a method may be executed in different order (or concurrently) without altering the principles of the present disclosure. Further, although each of the example embodiments is described above as having certain features, any one or more of those features described with respect to any example embodiment of the disclosure may be implemented in and/or combined with features of any of the other embodiments, even if that combination is not explicitly described. In other words, the described example embodiments are not mutually exclusive, and permutations of one or more example embodiments with one another remain within the scope of this disclosure.